V 


EXCHANGE 


The  Thermal  Decomposition 

of 
Oil  Shales 


DISSERTATION 


SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS  FOR 

THE  DEGREE  OF  DOCTOR  OF  PHILOSOPHY  IN  THE  FACULTY 

OF   PURE   SCIENCE,  COLUMBIA  UNIVERSITY 


BY 
Ernest  Elmer  Lyder,  B.S.,  M.S.,  A.M. 


NEW  YORK  CITY 
1921 


The  Thermal  Decomposition 

of 
Oil  Shales 


DISSERTATION 


SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS  FOR 

THE  DEGREE  OF  DOCTOR  OF  PHILOSOPHY  IN  THE  FACULTY 

OF   PURE   SCIENCE,  COLUMBIA  UNIVERSITY 


BY 
Ernest  Elmer  Lyder,  B.S.,  M.S.,  A.M. 


NEW  YORK  CITY 
1921 


ACKNOWLEDGMENT 

The  author  desires  to  express  to  Dr.  Ralph  H.  McKee  his 
sincere  thanks  for  direction,  supervision,  and  encourage- 
ment throughout  this  work.  It  was  at  his  suggestion  that 
the  problem  was  undertaken. 

DEPARTMENT  OP  CHEMICAL  ENGINEERING 
COLUMBIA  UNIVERSITY 


The  Thermal  Decomposition  of  Shales. 
I— Heat  Effects 

The  methods  of  recovering  oil  from  oil  shales  are  discussed 
in  so  many  recent  articles  that  they  need  not  be  repeated 
here.  Suffice  it  to  say  that,  at  present,  the  only  known 
methods  involve  the  principle  of  destructive  distillation.1'2'3-* 
This  being  the  case,  some  of  the  factors  involved  in  the 
thermal  decomposition  of  shale  have  been  studied.  The 
results  of  this  research  will  be  published  in  two  papers. 
The  present  one  deals  with  the  manner  in  which  the  shale 
decomposes  under  the  influence  of  heat,  while  the  subse- 
quent article  describes  a  method  for  the  determination  of 
the  heat  of  reaction  involved  when  the  organic  material  of 
the  shale  decomposes  to  form  oil. 

ORIGIN  OF  OIL  SHALES 

DEFINITION — Oil  shale  is  defined4  as  an  argillaceous  or 
shaley  deposit  from  which  petroleum  may  be  obtained  by 
distillation  but  not  by  trituration  or  treatment  with  solvents. 
The  term  is  also  applied  to  those  shaley  deposits  which  are 
saturated  with  asphalt  or  petroleum  and  from  which  the 
bituminous  matter  can  be  removed  by  such  solvents  as  carbon 
bisulfide  and  benzene,  but  the  term,  as  ordinarily  under- 
stood and  in  the  sense  in  which  it  is  used  throughout  this 
paper,  excludes  the  oil-bearing  shales  and  applies  only  to 
those  which  contain  little  or  no  bitumen  soluble  in  the  or- 
dinary organic  solvents. 

The  chemical  composition  of  the  oil-forming  materials 
from  which  the  oil  is  produced  is  little  understood.  Professor 
Crum  Brown  has  given  the  name  "kerogen"  to  the  material 
in  Scottish  shale  Which,  on  destructive  distillation,  yields 
oil.4  He  defines  it  as  neither  petroleum  nor  bitumen,  but 
a  substance  yielding  petroleum  and  ammonium  compounds 
on  distillation. 

NOMENCLATURE — Some  confusion  is  apt  to  arise  as  a 
result  of  the  designations  of  the  various  products  formed 
one  from  the  other.  A  bitumen  is  usually  defined  as  a 
natural  or  pyrogenous  hydrocarbon  which  may  or  may  not 
contain  oxygen,  nitrogen,  or  sulfur,  and  which  is  largely 

*  Numbers  refer  to  bibliography  on  page  18. 

(5) 


soluble  in  carbon  bisulfide.  Abraham5  calls  the  insoluble 
compounds,  such  as  are  found  in  shales,  pyrobitumens. 
Engler6  classifies  as  bitumens  the  whole  series  of  products 
which  are  formed  from  the  decomposition  of  vegetable  or 
animal  fats,  waxes,  or  residues.  This  latter  definition 
would  include  the  insoluble  substances,  such  as  kerogen  and 
pyrobitumens,  as  well  as  the  soluble  ones.  Since  the  terms 
"kerogen"  and  "pyrobitumen"  have  been  used  to  designate 
the  insoluble  substance,  the  word  "bitumen"  in  this  paper 
will  be  restricted  to  the  soluble  hydrocarbons. 

INSPISSATED  PETROLEUM — Little  is  known  as  to  the 
origin  or  nature  of  kerogen  or  other  organic  material  in 
the  shale.  That  all  of  the  organic  or  carbonaceous  matter 
does  not  produce  oil  is  known.7  E.  H.  Cunningham-Craig 
attributes  the  origin  of  kerogen  to  inspissated  or  dried-up 
petroleum.  He  concludes  that  the  oil  shale  stratum  is 
a  former  oil-bearing  formation  which,  under  the  action 
of  heat,  has  evaporated  and  dried  up,  leaving  petroleum 
residues  which  have  become  insoluble  by  polymerization.4 
Other  authorities  are  not  inclined  to  accept  this  theory, 
as  they  see  no  substantial  evidence  of  petroleum  having 
passed  through  the  formation. 

RESIN  THEORY — H.  R.  J.  Conacher,8  on  the  basis  of 
microscopic  examination,  describes  the  organic  matter 
in  the  shale  as  (1)  carbonaceous  bits  of  plants  with  occa- 
sional small  spores,  (2)  yellow  bodies  believed  to  be  algae, 
spores,  or  oil  globules,  (3)  shells  of  minute  crustaceans, 
and  bones,  teeth,  and  scales  of  fish,  and  (4)  sand  grains. 
Shale  portions  rich  in  animal  remains  give  small  yields  of  oil. 
Those  rich  in  vegetable  remains  give  a-gFeater  yield  of  oil. 
The  yellow  bodies  in  the  foregoing  tests  are  considered 
vegetable  matter.  New  Brunswick,  Colorado,  and  Utah 
shales  do  not  contain  many  of  these  yellow  bodies.  They 
are  thought  to  be  fragments  of  resins  set  free  by  decay  and 
oxidation  of  materials  of  which  they  were  once  a  part.  Sol- 
ubility of  resins  decreases  with  age;  therefore  the  theory 
that  failure  to  extract  them  by  solvents  proves  that  these 
bodies  are  not  resins  is  of  no  value.  Resinous  materials 
from  coal  yield  on  oxidation  the  same  products  as  obtained 
from  torbanites. 

Jones  and  Wheeler9  report  that  by  extraction  of  common 
coal  with  pyridine  and  reextraction  of  this  extract  with  chloro- 
form, coal  can  be  resolved  into  cellulosic  and  resinic  parts. 
On  distillation  of  the  former  they  obtained  phenols,  while 
the  latter  gave  paraffins,  defines,  and  naphthenes. 

ANOTHER  THEORY— D.  R.  Stuart10  is  inclined  to  think 
that  the  kerogen  may  come  from  different  kinds  of  organic 
matter,  either  animal  or  vegetable,  by  the  action  of  microbes 
under  special  conditions,  the  product  depending  upon  the 
microbe  and  the  starting  material.  The  kerogen,  on  the  other 
hand,  may  be  the  remains  of  certain  kinds  of  vegetable 

(6) 


matter,  like  pine  pollen  or  lycopod  spores.  He  actually 
prepared  oils  very  similar  in  properties  to  shale  oil  by  the 
distillation  of  a  mixture  of  75  per  cent  fuller's  earth  and  25 
per  cent  lycopodium  spore  dust. 

ORGANIC  REMAINS — Engler  u  chooses  to  fit  the  origin 
of  the  pyrobitumens  of  shales  into  the  whole  scheme  of 
bitumen  and  petroleum  formation  from  organic  remains, 
successive  polymerization  and  decomposition  playing  a 
very  important  part  both  in  the  character  of  the  petroleum 
and  in  the  bitumen  formed. 

By  the  decay  of  fats,  waxes,  and  other  animal  and  plant 
remains  there  are  produced  free  fatty  acids,  wax  esters, 
and  hydrocarbons  of  the  type  of  adipocere,  montan  waxes,  and, 
perhaps,  ozokerite.  These  are  soluble  in  benzene,  carbon 
bisulfide,  etc.  Part  of  this  material  may  condense  and  polym- 
erize to  form  what  Engler  chooses  to  call  polybitumens. 
These  are  infusible  and  insoluble,  and  are  found  in  nature 
as  the  insoluble  part  of  the  Scottish,  Austrian,  and  Autun 
shales.  These,  under  the  action  of  heat,  may  go  over  to 
soluble  bitumens,  small  amounts  of  which  are  always  found 
in  the  shale,  and  which  may  also  be  found  in  nature  as  mal- 
thas, etc.  Disintegrating  further  under  the  action  of  heat 
and  pressure,  these  compounds  go  over  to  natural  petroleum 
as  we  find  it  in  wells,  and  this,  on  polymerization,  yields 
the  heavy  asphalts. 

CLASSIFICATION 

Shales  differ  considerably  among  themselves.  Upon 
destructive  distillation,  they  yield  products  differing  in 
character  even  though  they  be  produced  under  similar  con- 
ditions. It  is  estimated  that  Elko  Nevada  shales  will  pro- 
duce paraffin  wax  to  the  weight  of  35  per  cent  of  the  total 
oil  recovered,  whereas  the  New  Brunswick  shale  oil  contains 
but  little  paraffin.  The  oil  from  the  latter  resembles  Cali- 
fornia crude.  An  attempt  to  classify  the  various  hydro- 
carbons in  these  shales  leads  to  some  confusion,  but  a  partial 
classification  on  the  basis  of  solubility  in  organic  solvents 
and  chemical  composition  is  possible. 

The  pyrobitumens,  which  form  bitumens  on  heating, 
may  be  further  subdivided  into  one  class  which  contains 
little  or  no  oxygen  and  another  which  does  contain  oxygen. 
Those  in  the  first  class  are  called  asphaltic  pyrobitumens 
because  they  resemble  asphalts,  which  contain  but  little 
oxygen.  They  are  infusible  and  insoluble,  and  include 
elaterite  wurtzellite,  albertite,  imposinite,  and  asphaltic 
pyrobituminous  shales.  The  New  Brunswick,  Nova  Scotia, 
and  Quebec  shales  are  of  this  type. 

The  nonasphaltic  pyrobitumens  are  those  which  contain 
oxygen  and  oxygenated  bodies,  but  are  also  insoluble  and 
infusible.  Into  this  class  fall  cannel  coals,  lignites,  tor- 
banites,  and  shales  containing  torbanite  material.  The 
Scottish  shale  belongs  in  this  category. 

(7) 


DISTRIBUTION 

Oil  shales  occur  in  various  parts  of  the  world  in  apparently 
unlimited  quantities.  In  Scotland  the  shale  oil  industry 
dates  back  to  1850.12  France  began  to  develop  shales  in 
Autun  even  before  the  Scottish  industry  existed.  New  Zea- 
land has  several  times  attempted  to  use  them.13  In  Australia 
several  large  deposits  and  some  very  rich  shales  occur.14 
In  Tasmania  there  are  extensive  deposits.14  In  Africa 
there  are  shales  in  the  Transvaal  and  in  Portugese  East 
Africa.15  Spain  and  Serbia  also  have  oil  shales.13  In  the 
western  hemisphere  they  are  to  be  found  in  various  parts 
of  South  America,13  in  Canada,16- 17>  18  and  in  the  United 
States.19  None  of  these  enormous  deposits,  except  the  Scot- 
tish oil  shales,  have,  as  yet,  been  worked  with  complete 
success. 

The  oil  shales  of  the  United  States  rival  in  quantity  the 
known  coal  deposits.  There  is  sufficient  oil  obtainable 
from  the  shales  of  Colorado,  Wyoming,  and  Utah  to  supply 
the  United  States  for  several  generations.20  Colorado 
alone  has  enough  shale  to  produce  58,000,000,000  barrels 
of  oil.21  When  it  is  remembered  that  less  than  8,000,000,000 
barrels  of  oil  have  been  taken  from  wells  in  this  country 
since  the  first  well  was  drilled  in  1859,  the  quantity  of  oil 
available  from  these  shales  begins  to  be  appreciated. 

Although  attention  is,  at  present,  centered  on  the  oil  shales 
of  Colorado,  Utah,  Wyoming,  and  Nevada,  it  is  only  because 
these  are  exceptionally  rich  in  oil-forming  material.  Other 
deposits  exist,22  and  as  methods  are  perfected  for  working 
shales  the  poorer  ones  will,  no  doubt,  be  utilized.  In  Ken- 
tucky there  are  quite  extensive  shale  beds  which,  though 
not  quite  so  rich  as  the  Colorado  shales,  yield  more  oil  than 
those  being  worked  in  Scotland  at  present. 

The  enormous  quantities  of  shale  available  for  oil  pro- 
duction is  the  factor  that  continually  encourages  investiga- 
tion in  the  face  of  all  the  difficulties  surrounding  the  problem. 

THE  PETROLEUM  SITUATION 

In  view  of  present-day  statistics  it  must  be  admitted 
that  the  future  of  petroleum  in  the  United  States  is  not 
encouraging.  The  figures  for  1920  show  that  some  110,000,- 
000  barrels  of  oil  were  imported  to  make  up  the  deficit  in 
home  production.  Fig.  1  illustrates  the  situation  as  it  stands. 

While  as  yet  the  maximum  production  of  petroleum 
in  this  country  has  not  been  reached,  it  will  be  seen  that 
the  consumption  is  much  greater  than  the  production,  and 
the  consumption  is  expected  to  increase.  It  was  in  1895 
that  the  first  commercially  practical  automobile  was  dem- 
onstrated, and  at  the  beginning  of  1920  there  were  8,000,000 
automobiles,  1,000,000  trucks,  and  300,000  tractors  in  use. 
Further,  it  is  expected  that  by  the  end  of  1921  there  will  be 
9,000,000  automobiles  and  trucks,  and  450,000  tractors 
in  use.  Aerial  navigation  is  yet  ahead,  but  may  be  expected 

(8) 


soon  to  consume  large  quantities  of  particularly  high-grade 
motor  spirit. 

That  oil  shale  can  be  utilized  to  make  up  the  deficiency 
caused  by  the  increased  consumption  of  petroleum  is  the 
opinion  of  our  best  authorities  on  the  subject.  In  this 
connection  we  may  quote  Dr.  Dean  E.  Winchester,23  formerly 
of  the  U.  S.  Geological  Survey: 

550 


Showing  Production 
Consumption  of 
Crude  Oil  in  the  U.S. 
since  1912 


1914         1916         1918       1920 

"Year 

FGI   1 

After  spending  nearly  five  years  in  studying  the  oil  shales  of 
the  western  part  of  the  United  States,  I  am  thoroughly  con- 
vinced that  the  day  is  not  far  distant  when  these  very  shales 
that  the  cattlemen  and  farmers  of  the  Rocky  Mountain  region 
have  sworn  at  so  often  because  they  make  neither  good  farm 
land  nor  good  range,  will  yield  oil  in  sufficient  amounts  to  pre- 
vent the  rapid  decline  on  our  total  production  which  is  imminent 
if  no  new  source  of  petroleum  is  developed.  There  seems  to  be 
every  indication  that  in  the  near  future  (perhaps  ten  years) 

(9) 


there  will  be  established  in  Colorado  and  Utah  an  industry  for 
mining  and  distilling  of  oil  shales  which  will  rival  in  size  any 
mining  or  manufacturing  industry  in  the  United  States. 

FIELD  OBSERVATION 

An  inspection  trip  to  the  Colorado,  Utah,  and  Nevada 
districts  during  the  summer  of  1920  revealed  the  fact  that 
considerable  work  of  a  certain  nature  is  being  done  toward 
the  development  of  these  shales.  Several  retorts  have 
been  built  in  the  field,  but  none  of  them  are  operating  in 
any  regular  way.  Some  are  small  one-unit  plants  operated 
for  demonstration  and  experimental  purposes  only.  Some 
of  the  schemes  will  probably  never  work  and  are  intended 
more  for  promoting  purposes  and  the  sale  of  stock  than 
for  actual  production  of  oil.  Others  are  making  every  ef- 
fort to  produce  a  retort  which  will  successfully  distil  these 
shales.  Almost  all  of  the  development  seems  to  be  toward 
the  perfecting  of  a  retort  which  will  produce  oil,  without 
consideration  of  the  character  and  quality  of  the  oil  produced. 
None  of  the  oil  is,  as  yet,  being  refined,  and  when  refining 
operations  are  begun  it  is  quite  probable  that  the  oil  will 
be  found  deficient  in  quality,  and  some  of  the  retorts  that 
are  furthest  advanced,  at  present,  may  have  to  be  redesigned 
completely  to  meet  the  necessity  of  producing  a  marketable 
oil.  Let  it  be  said  that  this  does  not  apply  to  all  of  the  plants 
in  the  field.  Some  are  studying  all  of  the  conditions,  each 
one  in  its  proper  relation  to  the  other,  and  are  making  definite 
progress. 

THERMAL  DECOMPOSITION  OF  SHALES 

Oil  shales  are  but  little  soluble  in  organic  solvents,  as  has 
been  pointed  out.  They  are  not,  therefore,  hydrocarbons 
of  the  type  of  gilsonite,24  grahamite,24  ozokerite,24  or  asphalt. 
Shales  must  be  distilled  to  recover  the  oil  and  ammonia  prod- 
ucts from  them.  The  oil  is  said  to  come  from  a  specific 
pyrobituminous  material,  and  not  from  the  entire  organic 
remains  in  the  shale.  From  Scottish  shale,  oil  is  said  to  come 
from  kerogen.  In  any  case,  upon  destructive  distillation 
of  a  number  of  different  kinds  of  pyrobituminous  substances, 
hydrocarbons  of  the  nature  of  paraffins,  defines,  and  aro- 
matics  are  produced.7' 26 

The  hydrocarbons,  when  distilled  off  and  fractionated, 
yield  low-boiling,  intermediate,  and  high-boiling  fractions, 
just  as  do  naturally  occurring  petroleums.  Many  retorts 
have  been  designed  to  distil  these  shales,  and  each  is  based 
on  the  designer's  conception  of  the  manner  in  which  the  shales 
decompose.  For  the  most  part  the  idea  seems  to  be  prevalent 
that,  upon  breaking  down,  the  kerogen  or  other  pyrobitumens 
yield,  directly,  petroleum  oils.  Many  think  that  they 
yield,  first,  gasoline-like  products;  second,  heavier  products, 
such  as  kerosene;  next,  gas  oil;  and  so  on  as  the  temperature 
increases.  Others  believe  they  yield  a  wide  range  of  products 
directly,  that  is  to  say,  each  molecule  of  kerogen  will  de- 

(10) 


compose  into  gasoline,  kerosene,  etc.,  in  essentially  one  step 
In  this  case  the  gravity  of  the  oil  should  not  appreciably 
increase  as  the  temperature  rises.  It  has  been  demonstrated 
in  this  work  that  neither  of  the  above  conceptions  is  correct. 
The  first  product  of  decomposition  was  found  to  be  a  heavy 
semisolid  or  solid  bitumen  which  is  soluble  in  benzene 
and  carbon  bisulfide,  and  it  was  found  that  the  formation 
of  the  petroleum  oil  is  a  result  of  the  cracking  of  this  heavy 
bitumen.  This  is  in  accord  with  Engler's  deduction26  that 
certain  pyrobitumens,  when  heated  to  certain  temperatures, 
become  soluble  in  organic  solvents.  Table  I  shows  some 
of  the  results  of  the  decomposition  of  materials  of  this  nature.27 

TABLE  I — INCREASE  IN  SOLUBILITY  OF  SHALE  UPON  HEATING 


-SOLUBLE  IN    BENZENE- 


Before  After  Heating 
Heating  Temp.  Additional 

SOURCE  Per  cent    °  C.          Duration  Per  cent 

Posidonomya shale  0.6         250       24  hrs.  0.34) 

from  Reutlingen  300       Additional  24  hrs.  3.24J     d-58 

400      Additional  24  hrs.  0.00 

Menilite  shale  from  0.85       300  0.5  hr  1.21)     , 

Strzytki,  Egst.  Glacia  350  Additional  24  hrs.  0.70^     2.31 

350  Additional  24  hrs.  0.40)      2-06 

Shale  from  N.  S.  Wales,     1 . 40       250  2  days  1 . 33  ) 

Australia  250  Additional     8  days  0.73) 

Shale  from  N.  S.  Wales,      1.40       300       2  days  28.50)     ofi  •> 

Australia  300       Additional     8  days %       7.80J 

Shale  from  N.  S.  Wales,      1.40       400  1  hr .  4 . 90 } 

Australia  400  Additional  2  hrs.  44.90  I    55.2 

400  Additional  2  hrs.  5.40  \ 

400  Additional  2  hrs.          0 . 00 ) 

If  this  deduction  is  correct  it  is  of  considerable  importance, 
and  if  proved  experimentally  would  define  methods  for 
shale  distillation  superior  to  the  ones  now  used.  Experi- 
mental work  was  carried  out  as  follows: 

EXPERIMENTAL  METHODS — The  finely  ground  shale, 
60-mesh,  was  placed  in  a  2-m.  iron  tube,  20  in.  long.  The 
tube  was  capped  at  both  ends  and  fitted  with  a  pressure 
gage.  The  whole  was  placed  in  a  rotary-type,  gas-heated 
furnace  in  which  it  was  possible  to  control  the  temperature 
very  accurately.  A  base-metal  thermocouple  was  also 
placed  in  the  tube  with  the  shale.  The  shale  was  heated 
in  this  apparatus  for  periods  of  time  ranging  from  1  to  8 
hrs.  It  was  then  taken  out  and  examined,  and  the  amount 
of  soluble  material  in  it  was  determined.  Observations  were 
made  on  the  temperature  and  pressure  as  the  heating  pro- 
gressed. 

It  was  found  that  in  some  cases  when  the  shale  was  heated 
for  6  hrs.  around  390°  C.,no  apparent  change  occurred. 
Little  gas  was  given  off,  as  was  indicated  by  the  fact  that 
the  pressure  remained  around  25  or  30  Ibs.  per  sq.  in.  Slight 
increase  in  solubility  was  noted,  but  the  shale  in  general 
maintained  its  hard,  rubber-like  texture.  In  other  experi- 
ments only  a  few  degrees  higher  (394°  to  398°),  and  in  one 
case  at  the  same  temperature,  decided  changes  were  noted. 
The  pressure  suddenly  rose  after  the  shale  became  heated  up, 
and  remained  around  100  Ibs.  per  sq.  in.  The  product  was 

(11) 


a  black  tar-like  mass  with  the  shale  residue  suspended  in  it. 
Upon  extraction  with  benzene  this  yielded  30  to  40  per  cent 
of  soluble  material,  as  compared  to  1.5  to  2 . 9  per  cent  on 
the  original  shale. 

It  was  not  possible  in  these  experiments  to  keep  the  tubes 
entirely  tight,  and  some  gas  and  vapors  usually  escaped. 
This  rendered  the  results  inconclusive.  Although  a  heavy 
product  was  obtained,  as  was  expected,  it  could  easily  have 
been  the  result  of  the  light  vapors  having  been  lost  by  dis- 
tillation, but  the  results  did  show  that  a  decided  change  was 
taking  place  in  the  shale,  and  this  at  a  quite  definite  tempera- 
ture. 

The  pyrometer  used  in  these  determinations  was  of  the 
ordinary  base-metal  type  and  was,  unfortunately,  equipped 
with  a  relatively  low  resistance  indicator,  which  rendered 
the  results  somewhat  questionable.  On  this  account  other 
means  of  studying  the  changes  that  were  taking  place  were 
adopted. 

The  final  method  was  to  distil  the  finely  pulverized  shale 
under  atmospheric  pressure  in  a  small,  electrically  heated, 
brass  retort,  shown  in  Fig.  2.  This  apparatus  had  the  ad- 
vantage that  the  temperature  could  be  controlled  accurately 
and  could  be  measured  to  within  the  experimental  error 
of  the  mercury  thermometer.  Also,  it  was  desirable  that 
the  distillation  be  made  under  atmospheric  pressure. 

The  run  was  made  as  follows:  About  25  g.  of  shale  were 
placed  in  the  retort.  After  the  temperature  of  the  metal 
bath  had  reached  that  at  which  it  was  desired  to  make  the 
run,  the  retort  was  set  in  place  and  allowed  to  heat  for  1  hr. 
20  min.  The  temperature  was  measured  by  means  of  a 
500°  C.  nitrogen-filled  mercury  thermometer  placed  in  the 
bath.  In  one  run  thermometers  were  placed  both  in  the 
retort  and  in  the  metal  bath  in  order  to  determine  the  tem- 
perature lag  through  the  shale.  It  was  found  that  the  center 
of  the  retort  attained  the  temperature  of  the  bath  within 
20  min.;  hence,  in  order  that  all  the  shale  might  stay  at  the 
desired  temperature  for  an  hour,  the  heating  was  continued 
for  1  hr.  20  min.  Preliminary  tests  had  shown  that  if  the 
shale  did  not  decompose  at  a  given  temperature  within  an 
hour  it  could  be  heated  at  that  same  temperature  for  several 
hours  with  no  apparent  change.  During  the  determination 
the  thermometer  was  not  used  in  the  retort,  as  shown  in 
the  figure,  but  was  placed  directly  in  the  bath.  It  was  only 
the  highest  temperature  that  was  of  interest  and,  of  course, 
this  could  be  more  easily  obtained  in  the  bath  than  elsewhere. 
The  oil  that  distilled  over  was  caught  and  measured. 

After  the  shale  had  been  heated  for  1  hr.  it  was  removed 
from  the  retort  and  extracted  in  a  Soxhlet  extractor  with 
carbon  bisulfide  to  remove  the  heavy  oil  or  bitumen  which 
had  formed  but  had  not  distilled  over.  This  bitumen  was 
freed  from  carbon  bisulfide  by  evaporation,  and  weighed. 

(12) 


Several  runs  were  made,  varying  the  temperature  by  small 
increments  each  time. 


FIG.  2 

DETERMINATIONS — The  shale  used  was  from  the  Parachute 
Creek  district  near  Grand  Valley,  Colorado.  It  had  the 
following  properties. 

MASSIVE  TYPE  SHALE 

Specific  gravity  1 . 60 

Specific  heat  0.25 

Moisture,  per  cent  0 . 13 

Volatile  matter,  per  cent  53.90 

Ash,  per  cent  47 . 00 

Oil  yield  per  ton,  gal.  63.50 

Solubility  in  CSz,  per  cent  1.96 

Run  I — This  run  was  made  as  described  above,  with  the  bath 
kept  at  from  373°  to  375°  C.  Eighty-five  hundredths  of  a  gram 
of  oil  distilled  over  and  1.45  g.  of  heavy  bitumen  were  extracted 
from  the  residue.  The  shale  was  but  slightly  changed  in  ap- 
pearance, and  had  not  lost  its  hard  massive  texture. 

(13) 


Run  2 — This  run  on  24  g.  was  like  the  previous  one,  except 
that  the  temperature  was  kept  at  384°  to  386°  C.  One  and 
three- tenths  grams  of  light  oil  were  obtained,  with  1 . 52  g.  of  heavy 
bitumen.  Little  change  was  seen  in  the  general  appearance 
of  the  shale:  it  was,  however,  slightly  darker. 

Run  3— This  run  was  made  at  398°  to  400°  C.  One  and  seven- 
tenths  grams  of  light  oil  were  collected  and  1.9  g.  of  bitumen. 
No  noticeable  difference  had  occurred  in  the  appearance  of  the 
shale. 

Run  4— A  run  at  425°  C.  yielded  4.2  g.  of  light  oil  and  4.93  g. 
of  heavy  bitumen.  The  character  of  the  residue  was  decidedly 
changed.  It  was  a  dry  coke-like  mass  which  could  be  easily 
pulverized  with  the  fingers  to  an  impalpable  powder,  the  original 
hardness  and  general  character  of  the  shale  having  been  en- 
tirely destroyed.  The  specific  gravity  of  the  bitumen  recovered 
was  about  1. 

Run  5 — This  decided  change  within  25°  suggested  that  val- 
uable information  might  be  gained  by  taking  an  intermediate 
step.  In  a  run  made  at  410°  C.,  the  amount  of  light  oil  was 
2.55  g.,  and  the  amount  of  bitumen  was  6.4  g.  This  bitumen, 
when  extracted  and  dried,  was  of  a  rather  rubber-like  texture. 
The  residue  left  in  the  retort  before  extraction  was  not  a  dried 
coke  mass  as  in  Run  4,  but  a  sticky,  tarry  conglomeration  which 
held  together  qu'te  tenaciously.  The  following  are  the  tabulated 
results  of  the  five  runs: 

Heavy  Oil 


Temp. 

Light  Oil 

(Bitumen) 

Total  Oil 

RUN 

°C. 

G. 

Per  cent 

G. 

Per  cent 

G. 

Per  cent 

1 

374 

0.85 

3.4 

1.45 

5.7 

2.30 

9.1 

2 

385 

1.30 

5.3 

1.52 

6.2 

2.82 

11.5 

3 

399 

1.70 

7.0 

1.90 

7.9 

3.80 

14.9 

4 

425 

4.20 

16.8 

4.93 

19.6 

9.13 

36.4 

5 

410 

2.55 

10.2 

6.40 

25.6 

8.50 

35.8 

No  correction  has  been  made  in  these  figures  for  the  original 
1.96  per  cent  soluble  in  carbon  bisulfide  before  heating.  The 
figures  would,  of  course,  bear  the  same  relation  to  each  other 
as  is  shown  above.  Fig.  3  is  the  graph  of  these  various  factors. 

INTERPRETATION  OF  RESULTS — The  interpretation  of 
the  results  of  the  experiments  just  described  is  plain  and 
important.  As  the  temperature  rises  in  each  successive 
determination,  increasing  amounts  of  oil  are  produced,  but 
the  quantity  is  rather  small.  At  between  400°  and  410°  C. 
the  curve  suddenly  rises,  showing  a  complete  destruction 
of  the  insoluble  kerogen  bodies  in  the  shale.  The  tempera- 
ture limits  are  seen  to  be  close.  This  would  indicate  that 
the  kerogen  has  a  decomposition  temperature  which  is  definite 
to  within  10°  C. 

Although  it  is  seen  from  the  curves  that  light  oil  is  always 
produced,  more  of  the  heavy  bitumen  than  light  oil  is  pro- 
duced at  the  lower  temperatures.  At  the  temperature  of 
decomposition,  i.  e.,  where  the  curve  starts  abruptly  upward, 
by  far  the  largest  part  is  heavy  bitumen,  and  during  de- 
composition large  quantities  of  heavy  oil  are  produced,  with 
no  corresponding  increase  in  light  oil.  If  light  oil  had  been 

(14) 


directly  produced  from  the  kerogen,  its  curve  would  have 
followed  the  heavy  bitumen  curve. 

CRACKING  OF  SHALE  OILS 

Another  item  of  importance  in  connection  with  these 
decompositions  is  that  the  shales  decompose  at  temperatures 
above  the  point  where  cracking  will  take  place  to  a  limited 
extent.  It  is  seen  that  even  at  375°  C.,  where  the  decom- 
position of  the  kerogen  was  relatively  slow,  some  light  oil 
was  formed,  but  cracking  became  rapid  at  almost  the  same 
temperature  as  that  at  which  the  shale  decomposes. 

The  break  and  descent  of  the  bitumen  curve  with  no  change 
in  the  total  quantity  of  oil  show  conclusively  that  the  heavy 
bitumen  is  decomposing  to  form  light  oils. 

Another  important  point  is  noted  here.  Various  dis- 
tillations of  this  Colorado  shale,  either  in  2-lb.  lots  or  20-lb. 
charges,  under  the  most  careful  conditions,  yielded  63  gal. 
of  oil  per  ton.  The  oil  obtained  had  a  specific  gravity  of 
0.921,  which  means  480  Ibs.  of  oil.  Add  to  this  20  Ibs. 
of  gas  obtained,  and  we  have  500  Ibs.,  or  25  per  cent  of  product 
per  ton  of  shale.  The  amount  of  product  obtained  when 
the  shale  was  heated  just  to  its  decomposition  temperature 
was  36  per  cent,  or  720  Ibs.  per  ton.  If  all  this  could  be  con- 
verted into  oil  of  0.921  specific  gravity,  it  would  yield  91.5 
gal.  of  oil  per  ton.  There  would,  of  course,  be  a  cracking 
loss  if  the  tar  were  converted  into  light  oils  after  its  removal 
by  solvents.  This  calculation  is  included  to  show  that 
the  maximum  hydrocarbon  yield  is  not  produced  by  the 
present  method  of  distillation  and  that  it  is  the  phenomenon 
of  cracking  that  produces  the  light  oils  with  which  the  in- 
dustry is  familiar. 

These  deductions  place  shale  oil  on  the  same  basis  as 
cracked  products  from  naturally  occurring  petroleum. 
It  has  been  shown  that  little  or  no  gasoline  is  obtained  from 
shale  as  a  primary  product.  The  gasoline  and  other  light 
cuts  from  shale  oil  are  in  many  respects  similar  to  gasoline 
obtained  by  cracking  petroleum.  They  are  highly  un- 
saturated;  the  boiling  point  is  low  for  a  given  gravity  com- 
pared with  that  of  paraffin  hydrocarbons;  they  are  a  mixture 
of  paraffins,  olefmes,  and  aromatics.7'25  This  would  indicate 
that  shale  oil  must  compete  with  cracked  products  as  to 
supplying  gasoline.  If  these  heavy  residua  can  be  cracked 
to  produce  motor  fuels,  other  heavy  residua  can  also  be 
utilized  for  the  same  purpose.  Development  will  be  along 
the  lines  of  improvement  of  cracking  processes  adaptable 
to  such  oils. 

Another  phase  of  the  situation  is  that,  although  gasoline 
is  the  product  most  in  demand  and  the  tendency  is  to  con- 
vert other  fractions  into  it,  all  of  the  crude  cannot  be  used 
in  this  way,  because  other  fractions,  such  as  kerosene,  gas  oil, 
lubricating  oil,  fuel  oil,  and  wax,  are  also  needed.  Conse- 
quently, it  is  the  shortage  in  crude,  and  not  that  of  gasoline, 
which  threatens.  As  high-grade  oils  (those  containing 

(15) 


large  percentages  of  gasoline)  decrease,  more  gasoline  will 
have  to  be  produced  by  the  cracking  of  heavy  fractions  of 
low-grade  oils.  As  cracking  processes  improve  and  heavy 
oils  are  more  in  demand,  shale  oil  will  compete  favorably 
as  a  product  which  can  be  worked  up  into  motor  fuel. 


370         380          390         400          410  *20         430 

Temperature  of  Bafh 

FIG.  3 

This  conception  has  an  important  bearing  on  the  com- 
mercial distillation  of  oil  shale.  It  shows  that  there  is  a 
certain  minimum  temperature  (which  will  probably  vary 
with  each  shale)  below  which  it  is  useless  to  heat  and  expect 
to  recover  oil  at  any  reasonable  rate.  Also,  when  the  tem- 
perature is  held  within  the  decomposition  range,  no  gasoline 
is  produced  as  a  primary  product.  It  is  fallacy  to  say  that 
a  certain  retort  will  yield  a  given  amount  of  gasoline  as  a 
primary  product.  The  retort  should  be  looked  upon  as  an 
apparatus  for  the  production  of  heavy  residua,  while  its 
efficiency  as  a  gasoline  producer  should  be  based  on  its 
adaptability  to  convert  these  heavy  oils  to  motor  fuel.  It 
is  not  meant  to  convey  the  idea  that  this  bitumen  or  primary 
product  should  be  removed  by  solvents  before  cracking; 
in  fact,  it  is  more  than  probable  that  the  most  effective 
way  to  crack  it  is  while  it  is  yet  mixed  with  the  shale  residue, 

(16) 


but  the  whole  problem  of  the  production  of  light  oils  should 
be  approached  from  the  point  of  view  of  the  cracking  of  heavy 
oils. 

With  this  information  as  a  guiding  principle,  a  conclusion 
may  be  reached  as  to  the  relation  that  shale  oils  will  bear 
in  making  up  the  shortage  due  to  the  increased  consumption 
of  petroleum. 

It  has  been  shown  that  the  light  oil  is  obtained  by  the 
cracking  of  heavy  products  which  are  formed  when  the 
shale  is  heated  to  a  quite  definite  temperature.  This  means 
that  the  shale  retort  of  to-day  which  produces  light  oils 
is  being  used  as  a  cracking  still.  A  little  consideration  will 
show  that  it  may  be  made  a  very  efficient  one.28 

Here  is  a  hydrocarbon  formed  from  the  decomposition 
of  microscopic  particles  of  material  disseminated  throughout 
a  mineral  mass,  and  this  hydrocarbon  is  formed  near  the 
temperature  at  which  it  is  subsequently  cracked  to  form 
light  oils.  This  insures  uniform  distribution  of  heat  not 
usually  met  with  in  ordinary  processes.  Further,  one  of 
the  most  difficult  problems  attending  the  cracking  of  oil  is 
the  removal  of  the  carbon  formed  and  deposited  in  the  still. 
In  the  Rittman  process  it  is  continually  scraped  down  by 
the  revolving  of  chains.  In  the  Burton  still  it  is  caught 
on  the  false  bottoms  of  the  still  and  thus  prevented  from 
caking  on  the  heated  zone.  In  the  case  of  a  shale  retort 
such,  for  instance,  as  those  used  in  Scotland,  it  is  being 
continually  removed  by  means  6f  a  mass  of  mineral  matter 
so  great  that  the  amount  of  carbon  is  insignificant. 

Without  the  use  of  steam  in  these  retorts  a  high  oil-yielding 
shale  will  yield  about  12  per  cent  of  carbon,  which  will  remain 
in  a  perfectly  dry,  finely  divided  condition  disseminated 
throughout  an  equally  dry  mineral  mass.  This  moves 
through  the  retort  without  difficulty,  and  no  carbon  troubles 
are  encountered. 

It  is  not  necessary  to  limit  the  amount  of  bitumen  passing 
through  the  retort  to  that  which  is  contained  in  the  shale. 
Other  heavy  residua,  such  as  bottoms  from  previous  runs 
or  from  petroleum  oil,  could  be  injected  into  the  retort 
and  cracked  to  light  oil  along  with  the  shale  residua.  The 
carbon  residue  would  be  materially  increased,  which  is  desir- 
able because  it  could  then  be  used  in  the  production  of  water 
gas  or  as  a  fuel  direct.  Shale  residues  from  the  straight 
distillation  of  shales  are,  at  present,  used  in  a  gas  producer 
for  the  production  of  fuel  for  retorting.21  They  are  also 
being  used  as  solid  fuels.  It  need  not  be  emphasized  that 
additional  carbon  would  make  them  more  valuable. 

CONCLUSIONS 

It  has  been  shown  that  the  pyrobitumens  do  not  decom- 
pose to  form  petroleum  oils  as  a  primary  product  of  de- 
composition, but  that  the  first  substance  obtained  is  a  heavy 
solid  or  semisolid  bitumen.  This  bitumen  is  formed  at 

(17) 


a  quite  definite  temperature,  the  formation  taking  place 
between  400°  and  410°  C.,  in  the  case  of  this  particular 
shale.  The  petroleum  oils  formed  from  the  shale  are  the 
result  of  the  decomposition  or  cracking  of  the  heavy  bitumen. 
BIBLIOGRAPHY 

1 — Thomas  Clarkson,  "Facts  about  the  Shale  Oil  Industry,"  Oil  and 
Gas  J.,  17  (1919),  60,  No.  52. 

2 — M.  J.  Gavin,  H.  H.  Hill  and  W.  E.  Perdew,  "Notes  on  the  Oil 
Shale  Industry,"  Bureau  of  Mines,  Bulletin,  1919. 

3 — Greene,  "Oil  Shales." 

4 — E.  H.  C.  Cunningham-Craig,  "Kerogen  Shales,"  Chem.  Trade  J., 
58  (1916),  360. 

5 — Herbert  Abraham,  "Asphalts  and  Allied  Substances,"  1918,   158. 

6— C   Engler,  "Das  Erdol,"    1  (1917),  35. 

7— H.  R.  J.  Conacher,  "The  Scottish  Oil  Shales,"  Petroleum  Rev., 
December  1916,  509. 

8 — H.  R.  J.  Conacher,  "Oil  Shales  and  Torbanites,"  Geol.  Soc.  Glasgow, 
Dec.  14,  1916,  164;  Geol.  Mag.,  4  U917),  93. 

9 — D.  T.  Jones  and  R.  *r.  Wheeler,  "Composition  of  Coal,"  J.  Chem. 
Soc.,  109  (1916),  767. 

10— D.  R.  Stuart,  "Chemistry  of  the  Oil  Shales,"  "Oil  Shales  of  the 
Lothians,"  Part  3.  Scotland  Geol.  Sur.  Mems.,  1912,  136. 

11 — C.  Engler,  "Formation  of  the  Chief  Constituents  of  Petroleum," 
Petroleum,  7  (1912),  399;  C.  A.,  6  (1912),  1221. 

12— H.  M.  Cadell  and  Grant  Wilson,  "Geology  of  the  Oil  Shale  Fields. 
The  Oil  Shales  of  the  Lothians,"  Part  1.  Scotland  Geol.  Sur.  Mems.,  1912, 
1-97. 

13 — Hardy  W.  Mansfield,  "Oil  Shales  and  Their  Occurrence,"  Pe- 
troleum Rev.,  34  (1916),  159,  199. 

14— Hardy  W.  Mansfield,  "Oil  Shales,"  J.  Inst.  Petroleum  Tech. 
(London),  2  (1916),  162. 

15 — "Transvaal  Oil-Shale  Deposits,"  M  in.  World,  34  (1911),  74-75; 
Petroleum  Rev.,  24  (1911),  147-148;  C.  A.,  5  (1911),  783. 

16— J.  W.  McGrath,  "Oil  Shales  of  Newfoundland,  "Petroleum  Rev., 
33  (1915),  209;  Can.  Min.  J.,  36  (1915),  493. 

17— "Bituminous  Oil  Shales  in  Canada,"  Min.  World,  37  (1912), 
202. 

18 — R.  W.  Ells,  Can.  Dept.  Mines  Joint  Report  on  the  Bituminous 
Oil  Shales  of  New  Brunswick  and  Nova  Scotia;  also  on  the  Oil  Shale  In- 
dustry of  Scotland,  1909. 

19— Dean  E.  Winchester,  "Oil  Shale  in  Northwestern  Colorado  and 
Adjacent  Areas,"  U.  S.  Geological  Survey  (Contributions  to  Economic 
Geology),  Bulletin,  641-F  (1916),  139. 

20— G.  E.  Mitchell,  "Billions  of  Barrels  of  Oil  Locked  up  in  Rocks," 
Geog.  Mag.,  33  (1918),  194. 

21— V.  C.  Alderson,  "The  Oil  Shale  Industry,"  1920,  31. 

22 — G.  H.  Ashley,  "Oil  Resources  of  the  Black  Shales  of  the  Eastern 
United  States,"  U.  S.  Geological  Survey,  Bulletin  641  (1917),  311. 

23— Dean  E.Winchester,  "Oil  Shales,"  J.  Frank.  Inst.,  87  (1919),  689. 

24— C.  Bardwell,  B.  A.  Berryman,  T.  B.  Brighton,  K.  D.  Kuhre, 
"Chemical  Properties  of  Utah  Hydrocarbons,"  Trans,  of  Utah  Acad.  of  Set., 
1  (1913),  78. 

25 — A.  H.  Allen,  "On  the  Relative  Proportions  of  defines  in  Shale 
and  Petroleum  Products,"  Analyst,  6  (1881),  177-180. 

26 — C.  Engler,  "Formation  of  the  Chief  Constituents  of  Petroleum," 
Petroleum,  7  (1912),  399-403;  C.  A.,  6  (1912),  1221. 

27— Herbert  Abraham,  "Asphalts  and  Allied  Substances,"  1918,  57. 

28— R.  H.  McKee  and  E.  E.  Lyder,  U.  S.  Pat.,  Application  No. 
381,440. 


(18) 


II.   Determination  of  the  Heat  of  Re- 
action Involved  in  Their  Thermal 
Decomposition 

The  solution  of  the  problem  of  the  recovery  of  petroleum 
oils  and  other  products  from  the  so-called  oil  shales  of  this 
country  must  be  based  on  exact  information,  such  as  the 
values  of  all  the  physical  constants  involved,  a  knowledge 
of  the  manner  in  which  the  oil-forming  material  decomposes, 
and  information  as  to  the  character  of  the  product  obtained 
under  varying  conditions.  Also,  since  it  is  apparently 
established  that  the  only  way  to  recover  petroleum  oils 
from  shales  is  by  thermal  decomposition, 1-2-3*  a  study  of  the 
heats  involved  and  the  primary  effect  of  heat  on  the  shale 
is  evidently  most  essential  to  the  intelligent  development 
of  the  industry.  It  has  been  the  object  of  this  research  to 
study  these  hitherto  little  known  factors  in  relation  to  their 
bearing  on  commercial  retorting. 

A  method  has  been  devised  for  the  determination  of  the 
amount  of  heat  involved  in  the  conversion  to  oil  of  the  or- 
ganic material  in  the  shale,  and  the  value  has  been  determined 
on  three  quite  different  types  of  shale.  It  was  found  that 
these  values  for  the  three  shales  used  ranged  from  421  to  484 
cal.  per  g.  of  oil  and  gas  produced. 

The  heat  conductivity  of  the  shale  has  been  determined 
for  this  work,  and  the  coefficient  of  thermal  conductivity 
has  been  found  to  be  0.00086,  expressed  in  c.  g.  s.  units. 

The  specific  heat  has  been  determined  and  found  to  be 
around  0.265  for  most  shales. 

Part  I  of  this  paper  has  shown  that  certain  fundamental 
conceptions  as  to  the  manner  in  which  the  organic  material 
decomposes  are  different  from  those  ordinarily  accepted. 
The  hitherto  generally  accepted  explanation  of  the  manner 
in  which  these  shales  decompose  is  that,  under  the  influence 
of  heat,  the  organic  material  breaks  down  from  a  high- 
molecular-weight,  insoluble  substance  to  form  petroleum- 
like  hydrocarbons.  These  hydrocarbons  increase  in  density 
and  boiling  point  as  the  temperature  rises,  that  is  to  say, 

*  Numbers  refer  to  bibliography  on  page  36. 

(19) 


the  first  product  of  destructive  distillation  of  shale  is  the 
light  hydrocarbon  oil  corresponding  to  gasoline  in  physical 
properties.  The  next  is  a  somewhat  heavier  product  like 
that  found  in  the  kerosene  fractions,  and  the  next  still  heavier, 
and  so  on  until,  finally,  heavy  residuents,  such  as  fuel  oil 
and  paraffin,  are  produced.  Part  I  has  also  shown  that  the 
organic  material  does  not  decompose  as  above  outlined, 
but  that  its  first  product  of  decomposition  is  a  heavy  solid 
or  semi-solid  bitumen  soluble  in  carbon  bisulfide,  whereas 
the  original  material  was  but  very  slightly  soluble.  The 
production  of  petroleum-like  oils  is,  then,  the  result  of  the 
decomposition  of  these  heavy  bitumens  by  cracking. 

The  importance  of  this  idea  is  that  it  places  the  production 
of  oil,  especially  gasoline,  from  shales  in  the  same  category 
as  the  production  of  gasoline  from  the  cracking  of  other 
oils.  It  should,  therefore,  promote  the  design  of  a  shale 
retort  along  this  line. 

At  the  beginning  of  this  work  little  or  nothing  was  known 
as  to  the  amount  of  heat  required  to  convert  to  hydrocarbons 
the  pyrobitumen  of  the  shale.  It  was  not  even  known  whether 
the  reaction  was  endothermic  or  exothermic,  and,  as  this 
could  easily  be  a  factor  of  prime  importance  in  the  design  of 
a  retort,  it  was  decided  to  determine  it  experimentally.  The 
design  of  the  apparatus  and  the  method  of  determining  this 
constant  are  described  in  this  paper.  Also,  there  have  been 
included  data  on  other  heat  factors,  such  as  specific  heat 
and  heat  of  vaporization.  Additional  information  can  be 
obtained  on  these  and  other  constants  by  consulting  the 
original  articles  referred  to. 

HEAT  FACTORS 

In  the  design  of  a  retort  it  is  desirable  to  know  the  quantity 
of  heat  that  must  be  added  to  bring  the  shale  to  the  distillation 
temperature,  to  cause  a  decomposition  of  the  organic  matter, 
and  to  distil  off  the  products. 

SPECIFIC  HEAT — The  specific  heat  will  vary  according 
to  the  composition  of  the  shale.  It  could  not  be  expected 
that  the  specific  heat  of  all  shales  would  be  the  same,  when 
it  is  considered  that  the  shales  are  mixtures  of  mineral  con- 
stituents of  varying  proportions,  through  which  an  organic 
material  is  disseminated,  also  in  varying  proportions.  The 
specific  heats  of  certain  shales  are  tabulated  below. 

Specific  °  C.  Temper- 

SUBSTANCE  Heat  ature  Range                AUTHORITY 

DeBeque  Shale  0.265  20-90  Bureau  of  Mines* 

Parachute  Shale  0 . 242  20-90  Bureau  of  Mines 

DeBeque  Shale  0.273  18-90  McKee  and  Lyder 

DeBeque  Shale  0.280  20-90  McKee  and  Lyder 

(Shale  Residue)  0.223  20-90  Bureau  of  Mines 

In  this  work  the  method  used  was  the  simple  method  of 
mixtures  as  ordinarily  applied.  The  average  of  the  raw  shale, 
which  is  probably  as  accurate  as  is  necessary,  is  0.265. 

HEAT  CONDUCTIVITY — The  heat  conductivity  of  the  shale 
should  be  expected  to  vary  with  composition  as  does  the 

(20) 


specific  heat.  At  our  request,  this  constant  was  determined 
on  four  samples  of  Parachute  shale  by  the  Bureau  of  Standards 
at  Washington,  D.  C.  The  method  used  was  one  that  they 
have  devised  for  the  determination  of  the  heat  conductivity 
of  poor  conductors,  such  as  asbestos  board.  It  should  be 
quite  accurate.  Briefly,  the  method  consists  of  placing  a 
slab  of  material  in  the  side  of  a  well  insulated  box,  heated 
from  the  inside,  and  comparing  the  loss  of  heat,  with  the 
sample  in  place,  with  that  of  a  sample  of  material  of  the  same 
dimensions  whose  conductivity  is  known.  The  samples  for 
the  experiment  were  prepared  by  having  a  stonecutter  saw 
them  from  a  large  lump  of  shale.  They  were  cut  7  in.  square 
and  0.75  in.  thick.  The  slabs  were  so  cut  that  in  conducting 
heat  from  one  face  to  the  other  the  heat  would  pass  perpendic- 
ular to  the  stratification  of  the  shale.  The  coefficient  of 
conductivity  as  determined  on  the  samples  was  0.00086 
(c.  g.  s.  units).  This  shows  that  the  shale  is  four  times  as 
good  a  conductor  as  paraffin  (0.0002),  about  one-third  as 
good  as  glass  (0.0025),  and  about  one-sixth  as  good  as  marble 
(0.005). 

This  value  is  quite  different  from  that  obtained  on  other 
shales  by  the  Bureau  of  Mines.  Their  value  is  0.0038. 4 

HEAT  OF  VAPORIZATION — The  heat  of  vaporization  is  a 
factor  of  considerable  uncertainty.  It  has  been  shown  that 
these  shales  decompose  into  a  heavy  tar-like  substance  and 
that  the  cracking  of  this  product  produces  shale  oil.  The 
heat  required  to  vaporize  this  heavy  tar-like  material  must 
include  the  heat  necessary  to  form  shale  oil  from  it.  At 
present,  little  can  be  said  as  to  this  value;  the  best  that  can 
be  done  is  to  include  the  true  heat  of  vaporization  of  similar 
oils.  Grafe  has  calculated  these  values  for  "Braunkohle" 
oils.6  The  following  are  his  data: 

Average1  Heat  of  Heat  to 

Boiling  Vapori-  Raise  to  Total 

Point  zation  B.  P.  Heat 

MATERIAL               °  C.        Sp.  Gr.          Cal.  Cal.  Cal. 

Light  crude                 216         0.883  86.5  82  168  5 

Heavy  crude               270         0.905            68.8  105  173.7 

Paraffin  oil                   328          0.920            63.3  130  193  3 

Heavy  paraffin  oil     346          0.933  53.8  138  191.8 
1  The  average  boiling  point  is  the  average  value  of  the  boiling  ranges 
of  all  of  the  5  per  cent  cuts  of  the  oil. 

The  heat  of  vaporization  of  Russian  petroleums  is  around 
75  cal.  per  gram.6  The  specific  heat  of  most  petroleum  oils 
may  be  taken  as  around  0.42. 

HEAT  OF  REACTION — The  heat  of  reaction  is,  in  this  case, 
the  heat  of  decomposition  of  the  kerogen  of  the  shale  into 
oil.  Heats  of  decomposition  are  usually  expressed  as  the 
number  of  calories  absorbed  or  evolved  per  gram  mole  of 
the  decomposing  substance.  In  the  present  case,  nothing 
is  known  of  the  molar  weights  involved,  and  it  is  therefore 
desirable  to  express  the  heat  of  reaction,  i.  e.,  the  heat  of 
decomposition,  either  in  terms  of  the  number  of  calories  pei 
gram  mole  of  shale  decomposed,  or,  better,  in  terms  of  calories 
per  gram  of  oil  (and  gas)  formed.  In  this  work  the  use  of 

(21). 


the  heat  of  reaction,  meaning  the  number  of  calories  per 
gram  of  oil  and  gas  formed,  has  some  advantages;  for  in- 
stance, it  permits,  at  once,  the  comparison  of  different  shales 
irrespective  of  the  amount  of  kerogen  they  contain. 

Heat  of  Combustion  Method — In  determining  the  heat 
of  reaction  of  organic  compounds  a  common  method  is  to 
determine  the  heat  of  combustion  of  the  original  material 
and  of  the  products  of  the  reaction.  Hess,  in  1840,  showed 
that  the  amount  of  heat  generated  by  a  chemical  reaction  is 
the  same  whether  it  takes  place  in  steps  or  all  at  once,  it 
being  only  the  initial  and  final  states  that  count  and  not 
the  path  by  which  the  reaction  proceeds.  If,  then,  a  given 
organic  substance  is  burned  to  carbon  dioxide  and  water,  and 
the  heat  involved  in  the  reaction  is  determined  by  a  calori- 
metric  method,  a  certain  value  is  obtained.  If,  on  .the  other 
hand,  the  substance  is  changed  by  heat  into  one  or  more  other 
substances,  and  the  heat  of  combustion  of  these  products  is 
determined  in  the  same  manner  as  above,  the  difference  in 
the  heats  of  combustion  will  represent  the  heat  that  it  took 
to  go  from  the  original  substance  to  its  decomposition  p  oduct. 
In  the  case  of  a  material  like  coal  where  the  products  can  be 
collected  and  the  heat  of  combustion  of  the  original  coal,  as 
well  as  of  all  of  its  products  of  decomposition,  determined, 
one  is  able  to  arrive  at  a  value  for  the  heat  necessary  to  de- 
compose the  coal.  Mahler  did  this  in  the  case  of  some  coals. 
In  a  substance  like  shale  the  experimental  problem  is  some- 
what difficult.  The  carbon  compound  or  combustible 
material  is  relatively  low,  ranging  from  10  to  50  per  cent. 
This  means  an  exceedingly  high  residue  or  ash.  If  these 
high  residue  materials  are  burned  in  an  ordinary  bomb 
calorimeter  the  combustion  is  nearly  complete,  and  constant 
results  are  generally  obtained;  yet  in  every  case  the  residue 
is  a  fused  jet-black  material  in  which  unburned  carbon  is 
in  evidence.  In  order  to  show  the  extent  of  this  combustion, 
runs  were  made  on  a  shale,  and  the  residue  from  a  bomb 
calorimeter  was  burned  in  a  Fleming  apparatus  of  the  type 
ordinarily  used  for  the  determination  of  carbon  in  steel. 
The  heat  value  of  the  shale  and  the  corresponding  correction 
for  carbon  is  shown  in  the  table.  In  making  this  calcula- 
tion, it  is  assumed  that  all  the  organic  material  left  in  the 
ash  is  there  as  amorphous  carbon  and  not  as  a  hydrocarbon. 
This  assumption  seems  fair,  in  view  of  the  very  high  temper- 
atures attained  in  the  bomb. 

Heat  of  Carbon 

Sample  Combustion                   in                                Correction 

No.  Cal.  per  Gram  Residue           Cal.  per  Gram  Per  cent 

1  2949  0.0031  6.80  0.23 

2  2954  0.0035  7.70  0.26 

3  2963  0.0038  8.30  0.28 
4^  2941  0.0036  8.50  0.29 

While  this  total  correction  is  small  on  the  original  shales 
and,  if  made  in  the  manner  described,  is,  no  doubt,  accounted 
for  to  within  the  experimental  error,  when  it  comes  to  making 
the  same  correction  on  the  residue  of  the  shale  after  the  oil 
has  been  distilled  off,  it  becomes  more  significant. 

(22) 


Heat  of  Carbon 

Sample          Combustion  in                                   Correction 

No.            Cal.  per  Gram  Residue  Cal.  per  Gram         Per  cent 

1  1319  0.014                      30.2                      2.3 

2  1318  0.016                     35.1                     2.5 

Here  there  is  an  error  of  2.5  per  cent  if  left  unconnected, 
and  one  somewhat  less  if  it  is  corrected.  Any  carbon  di- 
oxide remaining  in  the  residue  after  combustion  would  ap- 
pear by  this  determination  as  a  corresponding  amount  of 
carbon,  but  no  evidence  of  carbonates  was  found  in  the 
residue  after  it  had  been  heated  in  a  bomb  calorimeter. 

A  further  objection  to  the  method  as  applied  to  the  shale 
is  that  there  is  a  large  percentage  error,  owing  to  the  small 
value  of  the  heat  of  combustion  of  the  residue  after  the  oil 
has  been  distilled  off.  From  the  second  table  it  is  seen 
that  only  1136  cal.  per  g.  of  shale  are  obtained;  this  may  be 
in  error  by  2  per  cent.  Another  disadvantage  in  this  con- 
nection is  that  it  is  differences  of  heat  which  are  being  con- 
sidered, and  the  differences  are  usually  small,  which  cor- 
respondingly increases  the  percentage  of  error  in  the  final 
result. 

After  making  several  preliminary  runs  by  this  method 
it  was  decided  that  the  errors  involved  were  too  great  and 
that  it  would  be  best  to  work  up  an  apparatus  in  which  the 
heat  of  reaction  could  be  determined  experimentally. 

Euckene  Me^od-*-Euchene,7  in  his  calculations  on  "Thermo 
Reactions,"  has  calculated  the  heat  quantities  involved  in 
the  decomposition  of  coal.  This  he  did  by  summing  up 
the  heats  used  and  those  consumed  in  the  commercial  dis- 
tillation, and  striking  a  balance  which  showed  that,  in  the 
ordinary  coal-gas  process,  heat,  though  it  may  be  small, 
is  liberated.  His  method,  which  was  somewhat  tedious 
and  subject  to  large  error,  was  briefly  as  follows: 

First,  he  determined  how  much  fuel  it  took  to  distil  a  given 
amount  of  coal,  and  the  heat  value  of  the  fuel  was  calculated 
from  its  elemental  composition.  To  this  heat  he  added  that 
which  was  recovered  in  the  process  from  the  formation  of  certain 
gases  which  are  formed  with  a  liberation  of  heat:  carbon  di- 
oxide, carbon  monoxide,  methane,  water,  hydrogen  sulfide,  and 
ammonia  are  the  ones  involved.  The  sum  of  these  two  quanti- 
ties would  give  him  the  total  amount  of  heat  available  for  the 
distillation  of  coal. 

The  heat  used  in  the  process  was  then  calculated  by  duly 
considering  the  heat  used  in  the  formation  of  such  gases  as 
ethylene,  benzene,  carbon  bisulfide,  and  cyanogen,  which  are 
formed  with  the  absorption  of  heat.  To  this  was  added  the 
heat  lost  in  the  hot  gases,  coke,  ash,  and  by  radiation.  By 
balancing  up  these  quantities  he  found  that  the  entire  process 
liberated  heat  to  the  extent  of  from  12.39  to  63.51  cal.  per  g.  in 
certain  English  coals. 

This  value  may  be  considered  to  fall  well  within  the  very 
large  experimental  error  of  such  intricate  calculations,  but 
the  work  of  Mahler,  referred  to  above,  shows  also  that  the 
heat  of  combustion  of  the  original  coal  is  greater  than  that 
of  the  products  by  some  254  cal.  per  g.  This  value,  while 
not  agreeing  with  those  of  Euchene,  is  in  the  same  direction 

(23) 


and  of  the  same  order  and  shows  that,  taken  as  a  whole, 
heat  is  liberated  in  the  processes. 

Qualitative — Some  evidence  as  to  the  intricacy  of  the 
reaction  may  be  gathered  from  the  work  of  Rollings  and 
Cobb8  on  coal.  While  their  work  was  purely  qualitative, 
it  shows  the  procedure  of  such  reactions.  The  method 
employed  by  these  workers  was  to  place  in  an  ordinary 
combustion  furnace  two  boats,  side  by  side,  one  containing 
the  coal  to  be  distilled,  and  the  other,  a  nonvolatile  inert 
coal  which  would  undergo  no  change  as  the  distillation  of 
the  volatile  coal  proceeded.  As  the  two  were  heated  up 
together,  the  change  in  temperature  was  measured  by  means 
of  placing  in  each  the  junction  of  a  differential  thermometer, 
such  as  is  used  in  metallurgical  work  in  determining  the 
transition  point.  If  the  volatile  coal  absorbed  or  evolved 
heat  and  the  other  did  not,  their  difference  in  temperature 
would  be  recorded  by  the  instrument,  but  as  long  as  both- 
rose  in  temperature  by  simply  heating  up  with  the  furnace, 
no  abnormal  deflections  would  be  noticed  in  the  recording 
instrument. 

By  this  method  they  showed  that  coal  went  through 
several  stages  of  decomposition,  some  being  accompanied 
by  exothermic  and  others  by  endothermic  reactions. 

Up  to  410°  C.  Reaction  endothermic 

410°  to  470°  C.  Reaction  exothermic 

470°  to  610°  C.  Reaction   endothermic  (CHt  evolved) 

610°  to  800°  C.  Reaction  exothermic  (H2  evolved) 

There  is  a  definite  similarity  between  these  results  and 
some  which  the  present  authors  have  obtained  by  an  entirely 
different  method.  A  small  brass  retort  (see  Part  I,  Fig.  2) 
containing  the  shale  and  a  1000°  F.  nitrogen-filled  thermom- 
eter was  placed  in  an  electrically  heated  bath  after  the 
temperature  of  the  bath  had  reached  a  rather  high  value 
(850°  F.).  The  temperature  of  the  bath  was  measured  by 
means  of  a  rare  metal  thermocouple,  calibrated  in  terms  of 
1000°  F.  thermometer.  As  the  temperature  rose,  oil  was 
formed  and  distilled  over,  and,  within  about  an  hour,  the 
entire  50  g.  of  shale  could  be  decomposed.  After  the  com- 
pletion of  the  run  on  shale,  a  residue  (the  same  shale  from 
which  the  oil  had  been  distilled)  was  run  in  the  same  manner, 
and  the  temperature  effects  in  both  runs  were  compared. 
The  results  of  this  experiment  are  graphically  represented 
in  Curves  I  and  II,  Fig.  1.  The  method  used  in  plotting  the 
data  was  to  plot  time  in  minutes  as  abscissa  and  the  tem- 
perature changes  as  ordinate,  and,  in  order  to  facilitate  plot- 
ting, the  AT7  was  taken  as  the  average  for  each  5  min.  Refer- 
ence to  the  curve  shows  that,  with  the  shale  in  the  retort, 
the  temperature  change  remained  constant  until  the  still 
reached  745°,  showing  that  no  appreciable  decomposition 
was  taking  place  and  that  the  still  was  simply  rising  in  tem- 
perature with  the  bath.  As  the  temperature  increased, 
however,  the  temperature  changes  became  smaller,  passing 

(24) 


to  a  negative  value  within  the  next  10  min.  As  the  heating 
continued,  the  temperature  change  again  approached  normal 
and  was  followed  by  another  drop.  It  then  rose  gradually 


693    703    7/7     733.752     766     718     789    793       RETORT  TEMPERATURE ,°F. 
7/0    737    757    775    789   S80  8ZO   86S    867      BATH  ••  °F. 

17     24     40     42     35      54    42      76      74      GRADIENT  °F. 


! 

CL 

RVE  JT-  BLANK 

fc 

•>  —  i 

^ 

>—  —  ( 

^ 

->  c 

AT-  IS  THE  AVERAGE  CHANGE  IN  TEMPERATURE 
(°F.)  FOR  EACH  FIVE  MINUTES 

668  684  699  7/5  730  745  755  758  764  770 

780  721  765  785  788  815  835  S35  856  842 

52  54  73  62  58  70  80  80  72  72 
6  K 


767  770  776  786  766  8/5 
857  359  857  857  657  857 
90  87  81  91  61  42 


RET  OPT  TEMP. 

BATH 

GRADIENT 


0  10       '       ?0  30  40  50 

TIME   IN  MINUTES 

Fro.  1 

to  the  end  of  the  run.  This  is,  of  course,  a  rough  measure- 
ment, but  it  indicates  at  least  two  distinct  stages  in  the 
reaction.  Attention  is  here  called  to  the  corresponding 
curve  for  the  run  on  the  residues.  It  will  be  noticed  that 
the  time  required  to  reach  approximately  the  same  tempera- 
ture (800°  F.)  in  the  case  of  the  residue  is  only  about  half 
that  in  the  case  of  the  shale.  About  4  g.  of  oil  were  obtained, 
and  Curve  I  must  be  assumed  to  represent  partly  the  latent 
heat  of  vaporization  of  this  oil;  but  the  large  difference  must 
be  taken  to  mean  that  the  heat  of  reaction  over  the  whole 
range  of  the  curve  is  endothermic,  and  that  the  rise  at  764° 
is  an  indication  of  an  exothermic  reaction. 

DESIGN  OF  APPARATUS  FOR  MEASURING  HEAT  OF 

REACTION 

Inasmuch  as  these  data  indicated  a  .measurable  heat  of 
reaction,  it  was  determined  to  design,  if  possible,  an  apparatus 
wherewith  its  value  could  be  accurately  measured.  The 
factors  entering  into  such  a  determination  are  as  follows: 

•  1 — The  heat  conductivity  of  the  material  is  very  small  (0.00086) ;  there- 
fore a  considerable  temperature  gradient  must  be  maintained  to  decompose 
a  particle  of  shale  at  some  distance  from  the  source  of  heat. 

2 — Unless  a  very  high  temperature  gradient  is  maintained  the  reaction 
will  take  place  very  slowly.  (It  extended  over  about  an  hour  in  the  experi- 
ment above  described.) 

3 — The  product  obtained  depends  in  character  upon  the  manner  in  which 
the  shale  has  been  decomposed. 

The  problem  was,  therefore,  to  design  some  sort  of  calorim- 
eter in  which  a  high  temperature  could  be  maintained 
while  the  shale  was  being  decomposed,  and  one  to  which 
large  amounts  of  heat  could  be  added  without  abnormally 
high  calorimeter  temperatures  being  produced;  that  is,  a 
temperature  change  of  more  than  10°  C.  was  not  advisable 
in  the  calorimeter,  and  accordingly  the  calorimeter  should 
be  so  designed  that  the  total  heat  added  would  not  raise  it 

(25) 


more  than  this.  The  calorimeter  should  also  be  such  that 
the  radiation  correction,  due  to  the  comparatively  long  time 
in  which  it  must  be  run,  could  be  calculated  with  a  fair  degree 
of  accuracy. 

DECOMPOSITION  CHAMBER — The  first  problem  undertaken 
was  the  design  of  a  suitable  decomposition  chamber,  and 
the  points  to  be  considered  in  this  connection  were  (1)  to 
be  able  to  measure  the  heat  energy  added  with  sufficient 
accuracy,  (2)  so  to  design  it  that  a  high  temperature  could 
be  maintained  while  the  decomposition  was  going  on  and 
yet  to  eliminate  conduction  and  waste  heat  to  the  surround- 
ing water,  (3)  to  arrange  the  apparatus  to  cool  as  quickly  as 
possible  after  the  reaction  ceased  and,  thereby,  decrease 
the  radiation  correction,  and  (4)  to  make  the  parts  substan- 
tial and  rugged  enough  to  stand  repeated  determinations. 

As  regards  the  first  requisite,  it  was  decided  to  use  the 
resistance  of  an  electric  current  as  the  source  of  heat.  At 
the  beginning,  the  assumption  was  made  that  the  heat  of 
reaction  would  be  relatively  large  and  that  it  would  be  suffi- 
ciently accurate  to  measure  the  energy  by  means  of  an  or- 
dinary ammeter  and  voltmeter,  and  it  was  believed  that  the 
line  current  in  the  building  was  sufficiently  steady  for  use. 
As  work  progressed  it  was  found  that  the  apparatus  gave 
only  3  to  5  g.  of  oil,  and  that  its  heat  of  reaction  was  so  small 
that  more  refined  methods  were  necessary.  The  current 
had  to  be  taken  from  sixteen  Edison  cells,  and,  in  order  to 
reduce  further  the  error  in  the  quantity  of  heat  supplied,  a 
copper  voltameter  was  substituted  for  the  ordinary  ammeter, 
and  the  voltmeter,  which  was  a  Weston  instrument,  was 
calibrated*  and  corrected  and  read  to  0.01  of  a  volt. 

The  decomposition  chamber  was  a  brass  cylinder  about 
1.5  in.  in  diameter. and  about  2  in.  long.  It  was  fitted 
with  a  center  tube  sealed  up  through  the  bottom  and 
extending  nearly  to  the  top.  This  center  tube  was  to  serve 
as  a  passage  for  the  oil  vapor  to  leave  the  retort,  to  be  con- 
densed and  collected  in  a  receptacle  fitted  to  the  bottom  of 
the  center  tube.  This  chamber  is  shown  as  A  in  Fig.  2, 
with  the  condensation  chamber  C  attached  to  the  bottom. 
All  joints,  were  hard  soldered,  so  that  the  apparatus  would 
stand  any  reasonable  temperature.  The  lid,  through  which 
ran  the  electrical  leads,  was  fastened  on  by  means  of  a  union 
joint. 

HEATING  ELEMENT — The  heating  element  of  the  apparatus 
proved  to  be  the  most  delicate  part  and,  at  first,  required 
frequent  renewal.  Great  difficulty  was  experienced  in  getting 
a  properly  insulated  heating  element  so  small  and  yet  sub- 
stantial enough  to  stand  constant  use.  This  was  finally 
accomplished  by  winding  a  fine  nichrome  (22-gage)  wire 
around  an  ordinary  alundum  extraction  thimble  and  cement- 
ing it  in  place  (the  wires  properly  distanced  from  one  another) 

*  This  instrument  was  calibrated  by  Dr.  F.  A.  Strauss,  to  whom  thanks 
is   extended. 

(26) 


by  means  of  alundum  cement.  The  resistance  of  this  wire 
was  so  high  that  it  was  found  best  to  wrap  two  wires  and 
connect  them  in  parallel.  This  permitted  the  use  of  fine 
wire,  making  possible  ease  of  wrapping  and  even  distribution, 
and  at  the  same  time  sufficient  current  to  effect  decomposi- 
tion. 

In  the  first  apparatus  made,  the  coil  was  large  enough 
just  to  fit  within  the  walls  of  the  retort,  it  being  the  intention 
to  place  all  of  the  shale  within  the  alundum  thimble  and 
to  heat  entirely  from  the  outside.  After  many  attempts  this 
was  given  up  because  (1)  more  heat  was  given  off  to  the 
walls  of  the  retort  than  was  utilized  by  the  shale,  and  (2) 
the  extremely  low  heat  conductivity  of  the  shale  and  the 
fact  that  it  was  all  relatively  far  from  the  outside  of  the 
retort  made  cooling  very  slow.  To  avoid  this  a  smaller 
heating  element  was  made  and  placed  in  the  center  of  the 
retort,  and .  the  shale  to  be  decomposed  was  placed  around 
it  instead  of  in  it,  as  in  the  previous  case.  This  improvement, 
more  than  any  other  one  thing,  made  possible  the  desired 
decomposition.  First,  it  caused  the  shale,  which  is  a  splendid 
insulator,  to  act  as  its  own  insulation  from  the  surroundings 
while  the  heating  was  going  on,  and,  second,  it  placed  the 
shale  near  the  surface  of  the  retort  where  effective  cooling 
could  be  accomplished  when  it  was  desired  to  bring  the 
retort  to  the  temperature  of  the  calorimeter. 

CALORIMETER — With  the  retort  thus  designed  and  tested 
as  to  the  amount  of  oil  that  could  be  recovered  in  a  given 
length  of  time,  etc.,  the  next  problem  was  to  find  a  way  to 
measure  the  heat  recovered  during  the  decomposition.  Of 
course,  an  ordinary  standard  calorimeter  would  suggest 
itself  as  the  most  likely  piece  of  apparatus  to  use,  and  it 
was  thought  that  in  this  connection  a  gas  calorimeter  of  the 
Junker  type  might  be  successful.  The  ordinary  bomb  type 
(Mahler,  for  instance)  held  only  2000  g.  of  water,  and  pre- 
liminary experiments  showed  that  heat  to  the  extent  of 
30,000  to  40,000  cal.  would  be  necessary  to  effect  sufficient 
decomposition  to  render  measurements  accurate.  With 
2000  g.  of  water,  therefore,  the  final  temperature  would 
be  from  15°  to  20°  C..  which  was  entirely  out  of  the  question, 
but  the  gas  calorimeter,  being  a  constant  flow  apparatus, 
seemed  to  overcome  this  disadvantage.  The  method  was 
to  insert  the  decomposition  chamber,  fitted  up  as  described, 
into  the  body  of  the  calorimeter  where  the  combustion  or- 
dinarily takes  place,  to  close  the  bottom  tightly  and  blow 
a  steady  current  of  air  through,  virtually  creating  an  arti- 
ficial product  of  combustion,  and  to  measure  in  the  ordinary 
way  the  heat  given  off  to  the  water.  This  failed  completely 
because  the  retort  cooled  so  slowly  in  the  current  of  air  that 
about  100  Ibs.  of  water  had  to  be  put  through  before  the 
retort  came  to  the  temperature  of  the  incoming  water. 
With  this  large  amount  of  water  the  small  error  due  to 

(27) 


temperature  .readings  would  be  of  the  same  order  as  the 
value  of  the  heat  of  reaction  sought. 

The  only  objection  to  the  use  of  the  bomb  type  calorim- 
eter was,  as  has  been  mentioned,  the  fact  that  it  did  not 
hold  enough  water,  and  it  seemed  that,  if  the  bucket  were 
removed  from  that  type  of  apparatus  (one  of  the  Emmerson 
makes),  the  insulation  of  which  is  a  large  Dewar  flask,  and 
the  flask  simply  filled  with  water,  the  capacity  would  be 
greatly  increased  and  no  serious  disadvantage  would  be 
incurred.  By  this  method  4000  g.  of  water  could  be  used 
and,  by  proper  insulation,  the  retort  could  be  heated  and, 
at  the  proper  time,  quenched  and  cooled  down  at  will. 

INSULATION — In  order  to  heat  the  retort  effectively  in  a 
body  of  water  it  was  necessary  to  insulate  it  very  completely 
and  to  be  able  to  quench  it  quickly  when  once  the  run  was 
complete.  To  accomplish  this  an  outside  shell,  also  made 
of  brass,  was  made  large  enough  to  fit  over  the  retort  and 
leave  a  0.5-in.  space  for  insulation.  This  space  was  loosely 
filled  with  woven  asbestos  cloth.  The  jacket  was  fitted 
with  a  screw  cover  with  insulated  lead  w  res  through  for 
carrying  the  current.  The  jacket  was  also  fitted  with  a 
side  tube,  F  in  Fig.  2,  connected  at  the  top  and  bottom. 
In  the  bottom  of  this  tube  was  placed  a  ball  valve,  and 
through  the  tube  was  fitted  a  plunger.  The  object  of  this 
arrangement  was  to  allow  the  apparatus  to  heat  up  with  the 


FIG.  2 

insulating  material  dry  and  then,  when  the  run  was  finished, 
to  pump  water  from  the  calorimeter  by  means  of  the  plunger, 
thus  bringing  the  retort  back  to  the  temperature  of  the  cal- 
orimeter as  quickly  as  possible.  This  pumping  arrangement 
worked  very  well. 

The  complete  apparatus  consisted  of  a  brass  retort  A, 
Fig.  2,  fitted  with  a  water-tight  cover  and  insulated  plugs 
through  which  the  electric  lead  wires  were  passed.  It  also 
had  a  center  tube  extending  nearly  to  the  top  and  3  in.  below 

(23) 


the  bottom  of  the  retort.  On  the  bottom  of  the  center  tube 
was  a  small  brass  receptacle  fitted  with  a  screw  cover,  and  an 
outlet  through  which  the  permanent  gases  could  escape. 

A,  the  retort  proper,  was  surrounded  by  a  brass  jacket 
large  enough  to  permit  the  insulating  material  (asbestos 
cloth)  to  be  placed  between  them  and  leave  space  for  water 
to  circulate.  The  outer  shell  or  jacket  was  fitted  with  a  side 
tube  containing  a  hand-worked  piston  pump  by  means  of 
which  water  was  circulated  through  the  apparatus  to  cool 
it  down  to  the  temperature  of  the  calorimeter.  The  whole 
decomposition  chamber  was  suspended  from  an  especially 
made  lid  to  the  calorimeter. 

PROCEDURE 

The  procedure  in  making  the  run  was  as  follows:  The 
retort  was  filled  with  a  weighed  amount  of  shale,  and,  after 
all  connections  were  made  to  prevent  the  water  from  getting 
into  the  decomposition  chamber,  the  whole  was  suspended 
from  the  lid  of  the  calorimeter,  immersed  in  a  weighed  amount 
of  water  (.4000  g.),  the  thermometer  adjusted,  and  the 
stirrer  started  as  in  a  bomb  calorimeter  determination. 
At  the  beginning  of  the  determination  the  temperature  of  the 
water  in  the  calorimeter  should  be  about  as  much  below  room 
temperature  as  it  will  be  above  it  when  the  run  is  finished. 
This  decreases  the  radiation  corrections.  After  the  decom- 
position chamber  and  parts  in  contact  with  the  water  had 
come  to  the  water  temperature  the  current,  which  should  be 
adjusted  to  about  7  or  8  amperes  at  16  volts,  was  turned  on* 
Half-minute  readings  were  taken  on  the  voltage  and  minute 
readings  on  the  water  temperature.  At  this  rate  of  supplying 
heat  the  current  may  be  left  on  about  23  min.  without  raising 
the  temperature  of  the  calorimeter  more  than  10°  C.  This 
will  decompose  shale  sufficient  to  furnish  2  to  6  g.  of  oil  and 
gas.  At  the  expiration  of  this  time,  the  current  was  turned 
off  and  water  admitted  by  raising  the  pump  plunger.  Water 
was  pumped  through  the  apparatus  continually  as  long  as  the 
temperature  rose.  The  decomposition  chamber  was  then 
removed,  and  the  oil  and  water  were  removed  from  the 
distillation  chamber  C.  The  shale  was  taken  out  of  the  retort 
and  extracted  with  benzene.  This  was  necessary  because 
the  larger  part  of  the  oil  had  not  distilled  over,  but  remained 
in  the  shale  as  a  tar-like  substance.  The  gas  collected  in  the 
bottle  D  was  run  into  a  Bunsen  specific  gravity  bottle  and  its 
gravity  determined.  From  its  specific  gravity  and  the  volume, 
the  weight  of  the  gas  may  be  determined. 

WATER  EQUIVALENT 

On  account  of  the  variations  in  the  kind  of  material  used 
in  making  the  parts  of  the  calorimeter  (glass  as  a  container, 
brass  for  retort  and  jacket,  alundum  heating  core,  asbestos 
insulating  material,  nichrome  resistance,  and  copper  leads) 
it  would  have  been  difficult  to  calculate  the  water  equivalent 
of  the  calorimeter  from  the  specific  heats  of  the  parts.  This 

(29) 


was  particularly  true  of  the  heat  taken  up  by  the  glass  contain- 
ing vessel.  It  was  a  large  double-walled  vacuum  flask  holding 
4000  g.  of  water,  the  whole  being  permanently  fastened  into 
the  felt  insulation  of  the  calorimeter  proper.  The  entire 
flask  was,  therefore,  not  heated  to  the  temperature  of  the 
water,  only  the  inner  wall  being  in  contact  with  it;  hence 
there  was  no  way  of  weighing  the  particular  portion  of  the 
flask  heated.  The  water  equivalent  could,  however,  be  de- 
termined by  methods  similar  to  those  used  in  the  determina- 
tion of  the  water  equivalent  of  an  ordinary  bomb  calorim- 
eter. The  method  was  to  heat  up  the  apparatus  with  all 
of  its  parts  in  place  and  under  the  conditions  under 
which  an  actual  run  was  made,  excepting  that  instead  of 
using  the  shale  on  which  the  heat  of  reaction  was  to  be  deter- 
mined, a  residue  from  a  previous  run  which  contained  no 
volatile  matter  was  placed  in  the  decomposition  chamber. 
Then,  knowing  the  weight  of  the  water  present  and  the  energy 
added,  the  water  equivalent  could  be  calculated.  The  cal- 
culations involved  in  determining  the  water  equivalent  were 
as  follows: 

Let  Hi  =  heat  added  during  the  process 

V  =  volts  (average  at  which  current  is  supplied) 
m  =  weight  of  copper  deposited  on  electrode  of  voltameter 
e    =  electrochemical  equivalent  of  copper,  0.0003294 
/    =  mechanical  equivalent  of  heat  in  cal.,  4.18 

Then    H,    - 


0.0003294  X  4.18 
Also  let    H2  =  heat  recovered  by  calorimeter 
W  =  weight  of  water  in  g. 
w    =  g.  water  equivalent  of  calorimeter 
ti    =  initial  temperature,  temperature  of  calorimeter 

0  C.   (corrected) 
tt    =  final  temperature  of  calorimeter  °  C. 

(corrected) 

M  =  weight  of  oil  and  gas  recovered 
Then         H2  =   (W  +  w)  (tt  —  fa) 

Water  equivalent  is  then  found  by  equating  the  values 
of  Hi  and  H2  and  solving  for  W 

(Vm)  —  W  (fa  — fa)  0.0003294  X  4.18 


0.0003294  X  4.18   fa  —  <i) 

By  this  method  w  was  found  by  two  determinations  to  be 
157  g.  and  163  g.,  or  an  average  of  160  g.  The  value  of  the 
weight  of  the  water  was  taken  to  be  4000  +  160,  or  4160  g. 

ERRORS  AND  CORRECTIONS 

RADIATION  LOSSES — In  the  actual  manipulation  of  the 
apparatus  the  time  taken  to  heat  the  shale  to  its  decomposi- 
tion temperature  and  to  transfer  all  of  the  excess  heat  to  the 
calorimeter  was  considerable.  On  an  average  it  was  from  40 
to  50  min.  and,  even  though  the  apparatus  was  well  insulated 
(by  a  vacuum  jar)  and  the  radiation  per  minute  was  relatively 
small,  yet  when  the  operation  was  extended  over  such  a  long 
time  the  radiation  factor  was  quite  large.  It  would  amount 

(30) 


to  as  much  as  0.1°  C.  This  would  mean  approximately  410 
cal.  on  the  total  run.  This  correction  could  be  largely  elimi- 
nated by  starting  the  experiment  as  far  below  room  tempera- 
ture as  it  would  be  above  room  temperature  at  the  finish  if  the 
time  were  the  same  during  which  it  remained  above  and  below 
room  temperature;  but  this  is  not  the  case.  At  the  start, 
assuming  that  the  system  was  4°  or  5°  below  room  tempera- 
ture, it  would  heat  up  with  only  the  normal  radiation  from  the 
room,  but  after  the  operation  was  finished  with  the  tempera- 
ture of  the  water  some  4°  or  5°  above  that  of  the  room,  the 
apparatus  cools  down  at  a  rate  which  depends  upon  the 
rapidity  with  which  the  heat  is  transferred  from  the  inside  of 
the  retort  to  the  water.  This  is  exceedingly  slow  and  the 
instrument  may  run  at  a  constant  maximum  temperature  for 
as  much  as  6  or  7  min.  Therefore,  the  calorimeter  may  re- 
main at  this  high  temperature  for  a  considerable  time. 

In  order  further  to  eliminate  the  radiation  losses,  a  cor- 
rection was  applied  each  time.  The  method  adopted  was 
the  graphical  one  used  by  the  Bureau  of  Standards  in  con- 
nection with  their  bomb  calorimeters.9  It  is  found  to  work 
out  very  well  in  the  latter  case,  and,  inasmuch  as  the  opera- 
tion is  similar  in  principle  to  that  applied  here,  the  cor- 
rection is  probably  the  most  applicable  one  to  be  had. 

Let  n  «=  Rate  of  rise  (or  fall)  of  temperature  at  start  of  experiment 

rt  =  Rate  of  fall  "(or  rise)  of  temperature  at  finish  after  all  of  heat 
has  been  dissipated  to  the  water 

h  =  tTime  at  which  current  was  turned  on 

tt  =  Time  at  which  temperature  begins  to  fall  after  operation  is 
complete 

ta  =  Such  a  time  that  the  total  heat  radiated  to  the  calorimeter 

from  the  surroundings  while  it  is  below  room  temperature  is 
exactly  equal  to  that  radiated  to  the  room  by  the  calorimeter 
when  it  is  above  room  temperature.  In  other  words,  it  is  the 
time  at  which  the  calorimeter  ceases  to  absorb  heat  and  starts 
to  radiate  it.  For  graphical  reasons  it  is  taken  to  be  0.6  of  the 
total  rise  of  the  calorimeter. 

Then  ri  X  (to —  /i)    Heat  absorbed  by  the  calorimeter  and  is,  therefore, 
added  to  the  initial  temperature  and  heat  radiated  by  the 
calorimeter  to  the  surroundings 
rt  X  (/2  —  ta)     This  is  added  to  the  maximum  temperature 

It  is  seen  that  these  two  temperature  corrections  tend  to 
equalize  one  another,  and  if  the  proper  conditions,  such  as 
starting  at  the  right  temperature  and  running  the  proper 
length  of  time,  could  be  established,  they  would  cancel  each 
other.  A  typical  set  of  data  on  Colorado  shale  is  included 
to  illustrate  the  manner  of  this  correction. 

Thus  it  is  seen  that  there  is  an  actual  correction  of  0.20  — 
0.13  =  0.07°  F. 

It  will  be  noticed  that  the  temperature  reached  a  maximum 
and  ran  along  constant  for  8  min.  The  question  might  arise 
as  to  whether  the  time  tz  should  be  taken  at  the  time  when  the 
temperature  reached  a  maximum  or  at  the  end  of  the  8  min. 
It  is  probably  advisable -to  take  it  at  the  end  of  the  8  min. 

(31) 


Grams 
Wt.     of     electrode                                84.5260 
Wt.  of  electrode    +    copper               87.2360 

Wt.  of  copper  deposited 

2.7100 

TIME 

TEMP.  °  F. 

VOLTS 

AMPS. 

3:44.30 

64.9 

•45 

64.98 

":46 

:47 

64.99 
65.00 

12.00 
12.00 

6.49 

12.03 

:48 

65.10 

11.95 

12.00 

:49 

65.20 

11.98 

6.49 

12.10 

:50 

65.35 

11.95 

12.00 

•51 

65.55 

12.00 

7.05 

* 

12.00 

:52 

65.80 

14.10 
14.05 

7.00 

:53 

66.05 

14.00 

14.00 

:54 

66.40 

14.00 

14.00 

:55 

66.70 

14.00 

7.05 

14.00 

:56 

67  .  20 

14.00 

14.00 

:57 

68.70 

13.98 

7.10 

14.00 

:58 

69.00 

14.00 

14.00 

:59 

69.60 

13.00 

13.00 

4:00 

70.10 

12.95 
12.75 

6.90 

•01 

70.60 

12.90 

' 

12.95 

:02 

71.20 

13.05 

7.00 

12.90 

:03 

71.80 

12.95 

7.00 

13.00 

•04 

72.25 

Current 
off 

Time 
17.5min. 

Av. 

13.  08  volts 

:05 

73.30 

•06 

74.40 

:07 

75.20 

:08 

76.60 

:09 

77.65 

•*1  1 

78.10 

:12 

78.35 

78.55 

•14 

78.85 

•15 

78.89 

•16 

78.95 

•17 

79.04 

79.10 

•19 

79.15 

:20 

79.20 

•21 

79.24 

•22 

79.26 

-.23 

79.27 

•24 

79.28 

•25 

79.29 

•26 

79.30 

•27 

79.30 

•28 

79.30 

:29 

79.30 

•30 

79.30 

•31 

79.30 

•32 

79.30 

•33 

79.30 

:36 

79.29 

79.26 

Ohms 

Resistance 
Resistance 

of  voltmeter 
added 

180.4 
60.0 

240.4 

TTrtl-forr^     = 

240.4  X  13.08 

=  17.41 

(32) 


DATA  (Concluded) 

Weight  of  electrode  =  2.7100  —  0.0271   =2.6829 
Initial  temperature  64 . 99  °  F. 

Stem  correction  0 . 00 

Calibration  correction  —  0  07 

ri(ta  —  h)  =  0.01  X  20  =  0.20°  0.20 


Corrected  initial  temperature  65 . 12 

Final  temperature  79 . 20 

Stem  correction  0 . 00 

Calibration  correction  —  0 . 07 

n(ta  —  h)  =  0.005  X  27  =  0.13            0.13 

Corrected  final  temperature  79 . 26 

because  the  retort  is  still  radiating  heat  to  the  water,  as  other- 
wise the  temperature  would  start  to  fall. 

VOLTMETER  RESISTANCE — Another  correction  became  nec- 
essary because  of  the  manner  in  which  the  determination  was 
made.  The  voltmeter  was  kept  in  the  circuit  continuously 
instead  of  plugging  it  in  when  it  was  desired  to  make  a  reading. 
This  was  done  because  the  readings  were  taken  every  half 
minute,  and  it  was  simpler  not  to  throw  the  voltmeter  out  of 
the  circuit  between  the  readings.  The  resistance  of  the  volt- 
meter was  known,  and  the  current  it  took  could  readily  be 
calculated.  This  amounted  to  the  equivalent  of  about  1  per 
cent  of  the  weight  of  the  copper  deposited  on  the  electrode. 
It  was,  therefore,  subtracted  each  time. 

The  method  was  subject  to  several  sources  of  error  which 
could  not  be  eliminated.  These  were  calculated  so  far  as 
possible. 

ERRORS  IN  HEAT  SUPPLIED — In  the  heat  supplied  the  first 
error  would  be  that  due  to  voltage.  The  readings  of  the 
voltmeter  were  taken  every  half  minute,  and  the  average  of 
these  was  the  voltage  used.  The  readings,  when  corrected 
by  applying  a  standardization  correction,  should  be  quite 
accurate,  but,  unfortunately,  the  batteries  used  were  not  in 
first-class  condition,  and  the  voltage  varied  somewhat.  The 
readings  were  made  to  0.01  volt,  which  is  approximately  1  in 
1600.  As  a  result  of  this  variation,  the  average  was  probably 
not  better  than  0.02  volt,  which  is  0.13  per  cent. 

The  second  error  is  that  due  to  the  amperage.  The  use 
of  a  copper  voltameter  upon  which  2.7  g.  of  copper  is  usu- 
ally deposited  renders  the  correction  extremely  low.  With 
customary  precautions  in  weighing,  the  weight  could  easily 
be  determined  to  3  in  10,000,  or  an  error  of  0.03  per  cent. 

Heat  losses  due  to  leads,  conductivity  of  alundum,  etc., 
would  probably  not  exceed  0.05  per  cent. 

Adopting  the  principle  that  the  most  probable  error  is 
represented  by  the  square  root  of  the  sum  of  the  squares  of 
the  respective  errors,  the  probable  error  would  be  0.14  per 
cent.  On  30,000  cal.  produced  this  would  be  42  cal. 

THERMOMETER  READING — As  regards  the  measurement  of 
the  heat  recovered  by  the  calorimeter,  the  largest  error  is, 
perhaps,  that  of  reading  the  thermometer.  The  thermometer 
used  (calibrated  Bureau  of  Standards,  No.  10,482)  was  grad- 
uated to  0.05°  F.  Readings  could  be  made  to  within  0.005° 

(33) 


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(34) 


F.  at  initial  and  final  temperatures,  meaning  that  the 
error  would  not  exceed  0.01  °  F.  or  0.005 °  C.  If  the  tempera- 
ture rise  was  70  (about  the  average),  the  error  was  0.07  per 
cent. 

It  has  been  shown  that  after  calculation  for  the  radiation, 
the  radiation  correction  is  relatively  small.  There  is  no 
definite  way  of  arriving  at  what  the  radiation  error  may  be 
after  calculation  but  it  is  certainly  within  0.005°  C.  This 
would  make  a  correction  of  0.07  per  cent. 

The  weighing  of  the  water,  evaporation  losses  etc.,  will  not 
exceed  1.5  g.,  which  on  4000  is  equal  to  0.03  per  cent.  Taking 
the  square  root  of  the  sum  of  the  squares  it  gives  0.10  per  cent. 
On  30,000  cal.  this  would  be  30  cal. 

The  maximum  error  due  to  subtraction  of  the  heat  recovered 
from  the  heat  added  equals  30  +  42  =  72  cal.  This  repre- 
sents only  the  maximum  actual  error  due  to  the  subtraction 
of  the  heat.  The  actual  value  on  the  heat  of  reaction  as 
finally  obtained  will  be  discussed  later. 

Table  I  is  a  summary  of  data  and  results. 

The  oil  recovered  was,  for  the  most  part,  a  heavy  tar-like 
mass  which  was  largely  left  in  the  retort  mixed  with  the 
shale  and  had  to  be  extracted  with  benzene.  This  is  the 
character  of  the  material  produced  during  the  first  stage  of 
decomposition  from  kerogen  to  shale  oil.  In  order  to  produce 
lighter  distillates,  etc.,  from  these  it  is  necessary  to  crack 
these  residua.  The  heat  of  reaction  is  then  the  heat  nec- 
essary to  change  the  kerogen  into  this  primary  product. 

In  determining  the  heat  of  reaction  of  these  materials  three 
quite  different  types  of  shale  were  used:  (1)  The  Colorado 
shale  which  yields  products  similar  in  constitution  to  a  mixed 
base  petroleum  oil  such  as  is  found  in  the  Mid-continent 
field;  (2)  the  Canadian  shale  which  is  more  like  an  asphaltic 
base  oil,  such  as  California  crude,  and  contains  but  little 
paraffin;  (3)  the  Nevada  shale  which  is  peculiar  in  that  it 
contains  very  large  percentages  of  solid  paraffin  wax. 

The  average  of  the  results  of  the  Colorado  shale  is  seen  to 
be  —421  cal.  per  g.  of  oil  and  gas  produced,  for  the  Nevada 
shale  it  is  —  465,  and  a  single  run  on  the  Canadian  shale 
shows  —484.  These  results  are,  within  the  experimental 
error,  practically  the  same,  showing  that  this  value  is  quite 
constant  regardless  of  which  shale  is  used. 

SUMMARY — PARTS  I  AND  II 

1 — An  experimental  method  has  been  devised  for  the  deter- 
mination of  the  heat  of  reaction  involved  when  these  organic 
materials  decompose  to  form  oil  and  gas.  This  factor  has 
been  determined  on  three  quite  different  shales  and  found  to 
range  from  -  421  to  -484  cal.  per  g.  of  oil  and  gas  produced. 
So  far  as  is  known,  this  is  the  first  apparatus  designed  for  the 
direct  determination  of  this  factor  in  shales  or  similar  bi- 
tuminous materials. 

2— It  has  been  generally  thought  that  the  organic  matter 
in  shales  decomposed  to  form  petroleum  products  as  the 

(35) 


primary  products  of  decomposition.  This  research  has  shown 
that  this  is  not  the  case,  but  that  the  primary  product  of 
decomposition  is  a  heavy  solid  or  semi-solid  bitumen. 

3 — The  decomposition  temperature  of  the  shale  material 
has  been  shown  to  be  quite  definite  and  is  within  a  range  of 
10°  C.  The  decomposition  takes  place  between  400°  and 
410°  C. 

4 — When  petroleum  oils  are  formed  from  shales  they  are 
not  formed  directly  from  the  pyrobituminous  material  in  the 
shale,  but  they  are  formed  by  a  cracking  process  from  the  semi- 
solid  bitumen  just  mentioned.  This  cracking  process  is 
similar  to  the  well-known  phenomenon  of  the  cracking  of 
petroleum  oils. 

5 — New  data  have  been  .compiled  on  the  heat  conductivities 
of  shale.  The  coefficient  of  conductivity  was  found  to  be 
0.00086,  expressed  in  c.  g.  s.  units. 

6 — The  experimental  facts  determined  have  shown  that 
it  will  be  possible  to  design  a  shale  retort  to  be  used  simul- 
taneously as  a  cracking  still  for  shale  bitumen  and  heavy 
residua  from  natural  petroleum. 

BIBLIOGRAPHY 

1 — Thomas  Clarkson,  "Facts  About  the  Shale  Oil  Industry,"  Oil  and  Gas 
J.,  17  (1919),  60. 

2— M.  J.  Gavin,  H.  H.  Hill,  and  W.  E.  Perdew,  "Notes  on  the  Oil  Shale 
Industry,"  Bureau  of  Mines  Bulletin  1919. 

3 — Greene,  "Oil  Shales." 

4 — M.  J.  Gavin  and  L.  H.  Sharp.  "Some  Physical  and  Chemical  Data  on 
Shales,"  Oil  and  Gas  J.,  19  (1920),  86. 

5 — E.  Grafe,  "The  Heat  of  Vaporization  of  Petroleum  Oils,"  Petroleum, 
5  (1910),  569. 

6 — C.  F.  Mabery  and  A.  H.  Goldstein,  "On  the  Specific  Heat  and  Heats 
of  Vaporization  of  Paraffin  and  Olefine  Hydrocarbons,"  Am.  Chem.  J.,  28 
(1902),  66. 

7 — Euchene,  Trans.  Internal.  Gas  Cong.,  Paris,  1910. 

8— Rollings  and  Cobb,  J.  Chem.  Soc.,  107  (1915),  1106. 

9— Bureau  of  Standards,  Scientific  Paper  230,  229. 


(36) 


VITA 

Ernest  Elmer  Lyder  was  born  at  Kansas  City,  Kansas, 
on  September  30,  1886.  At  the  age  of  nine  he  moved  with 
his  parents  to  Paola,  Kansas,  where  he  received  his  elementary 
and  high  school  education. 

In  September  1909  he  entered  the  University  of  Kansas 
and  in  1913  received  from  that  institution  the  degree  of 
Bachelor  of  Science  in  Chemical  Engineering. 

After  graduation  he  was  employed  by  the  University  in 
the  capacity  of  research  assistant  in  the  department  of 
State  Chemical  Research.  During  the  first  year  he  made  an 
investigation  of  the  salt  deposit  of  the  state.  This  work 
is  being  published  by  the  Kansas  State  Geological  Survey. 
The  following  year  and  one  half  he,  in  conjunction  with  Dr. 
H.  C.  Allen,  made  a  chemical  survey  of  the  natural  gases 
of  Kansas  and  Oklahoma.  This  work  was  published  as 
Bulletin  No.  3.  of  the  University  of  Kansas.  .  During  this 
time  at  the  University  sufficient  'additional  graduate  work 
was  done  for  the  degree  of  Master  of  Science. 

In  January  1916  he  went  to  Bartlesville,  Oklahoma,  as 
Chief  Chemist  for  the  Empire  Gas  and  Fuel  Company. 
This  position  was  held  until  October  1917  when  he  came  to 
Columbia  University  to  study  in  the  departments  of  Chem- 
istry and  Chemical  Engineering.  Two  and  one  half  years 
have  been  spent  in  graduate  work  in  this  institution.  The 
degree  of  Master  of  Arts  was  granted  in  October  1918. 


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